Construction of Supramolecular Complexes via Tandem Claisen Rearrangement and Their Functions

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Not only macrocyclic but also noncyclic compounds having plural amide, catechol, and/or phenolic groups were synthesized in good yields via tandem Claisen rearrangement (TCR). Macrocyclic compounds (amidecrownophanes) formed supramolecular complexes with dihydrogen phosphate and fluoride ions exhibiting specific fluorescent emission.Noncyclic and macrocyclic compounds after TCR formed boron complexes by the reaction with sodium borohydride in high yields. These boron complexes were found to emit strong fluorescence in the range of 400 to 500nm. In particular, the fluorescence intensity of the macrocyclic boron complexes drastically increased depending upon the ring size of macrocycles when lithium ion was added to the solution.On the other hand, tripodands having three arms were prepared which can converted into the compounds having plural hydroxyl groups by TCR. They can react with Ti (IV) metal ions to form cryptand-type 1:1 complex. In addition, the cryptand-type metallo-supramolecular complex can include selectively metal ions and ammonium ions into the cavity. Besides, it was also found that the tripodands after TCR can include anion species. Noncyclic compounds having catechol moiety after TCR were prepared. They can make 3:1 complex with Ti (IV) ion. The structuire was successfully cleared by X-ray structural analysis and NMR spectroscopic methods.